Fungicidal composition



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United States Patent FUNGICIDAL COR [POSITION Charles C. Yeager, GlenEllyn, Ill., assignor to Scientific Oil Compounding Company, Inc., acorporation of Illinois" N Drawing. Application August 26, 1954,

. Serial No. 452,448

24 Claims. (Cl. 260-102) This invention relates to novel reactionproducts of a complex metal ammine salt of a rosin amine and a waterinsoluble carboxylic acid soap, the reaction to obtain this productbeing carried out in the presence of a quinoline. The novel reactionproducts so obtained have improved fungicidal and insecticidal uses andthe reaction products form solutions which are relatively light in colorto thereby' extend the uses of these products.

In my copending application entitled Fungicidal Composition, Serial No.389,159, filed October 29, 1953, I have described and claimed metalrosin, ammonium phenoxide complexes reacted with water insolublecarboxylic acid' soaps in the presence of a quinoline and I have furtherdescribed the high fungicidal activity of these products on plants(botanical), textiles, paper, leather, wood, sealers, lacquers, etc. Inthe treatment of textiles, paper or other sheet material with thesenovel compounds or in the incorporation of these novel compounds invarnishes, clear lacquers, sealers, or in the use of these new compoundsfor the treatment of vegetation to combat pest infestation, the presenceof undesirable extraneous color in the compositions containing thecompound presents a problem which may frequently limit the usefulness ofthese compositions. The problem was eifectively solved in my cope'ndingapplication Serial No; 389,159, particularly in the case where the metalof the rosin ammonium phenoxide complex is reacted with a copper soap'by carrying out the reaction in the presence of a quinoline.

I have found that it is possible to entirely omit the use of phenolsirrthe'manufacture of the finished product containing the complex metalammine salt of a rosin amine and the water insoluble carboxylic acidsoap by the present invention. Surprisingly, the formulations of thepresent invention in which themetal rosin ammonium phenoxide complex issubstituted by the complex metal ammine salt of a rosin amine providessubstantially as effective fungicidal protection as in the compositionswherein the phenoxi'de cdmplex is present. I have found that the compiermetal ammine salt of arosin amine reactedwith a water insolublecarboxylic acid soap in the presence of a quinoline produces an enhancedfungicidal eflicacy which is beyond that which can be attributedto theefiicaey of the components separately and substantially equivalent tothat of the compositions containing these ingredients i-neluded with thephenoxide complexing agent interacting with the rosin amine.

Further, the novel reaction products in accordance with the invention,particularly in the casewhere the insoluble carboxylicacid soap is asoap of copper, are of a light color. The deep blue color which existsinthe absence of quinoline and" which hascaused a dyeing problemparticularly where khaki shades are used is obviated in the presentproducts due to the presence of a quinoline in the reaction. It ispossible to dye textile and other fabrics to any desired khaki shadereadily. The omission of the phenol, above mentioned, in the manufactureof the product of the invention simplifies the manufacturing process.

ice

In general, the novel reaction products of the resent invention areprepared by reacting a complex metal arir-' mine salt of a rosin aminewith a water insolublesoap of a carboxylic acid in the presence of aquinoline, at an elevated temperature at least sufficient to place thereactants into homogeneous solution. The metal of the complex may benickel, copper, cobalt, zinc, aluminum,

silver, iron, chromium, mercury or other metal whose's'a-lt zincacetate, the acetates of the other named metals, and

the formate, chloracetate, bromoacetate, chloride, sulfate, borate,carbonate, thiocyanate, etc., salts capable of forming complexes withammonia. The quinoline may beany quinoline, substituted orunsubstituted, such asquinoline',v isoquinoline, quinaldine,4-chloroquin0line, 6 -nitroquin'oline, 7-nitroqu'inoline,6-methoxyquinoline, 8-methoxyquinoline, Z-hydroxyquinoline,4-methyl-2-hydroxyquinoline, 4-hydroxyquinoline,2-rnethyl-4-hydroxyquinoline,5 hydroxyquinoline, 6-hydroxyquinoline,7-hydroxyquinoline, 8-hydroxyquinoline, etc. The preferred quinoline's'are isoquinoline and 8'-hydroxyquinoline. The reaction may be carriedout at a temperature in the order of about 250 to 400 F. Lowertemperatures maybe used, but at a sacrifice of time. Highertemperatures, up to the lowest decomposition temperature of thereactants, may be used, if desired.

The proportions of the complex metal ammine salt of a rosin amine and ofthe water insoluble soap reactants may be varied widely, as desired.Thus, stoichiometri'cal proportions of these reactants or an excess ofone with respect to the other may be used. With respect to thequinoline, the proportions thereof may vary widely, from about 1.5% to14% by weight based on the weight of the complex metal ammine salt of arosin amine.

The complex metal ammine salt of a rosin amine may be introduced as suchinto the reaction with the water insoluble soap and the quinoline or itmay be formed in situ in the reaction mix. The in situ reaction ispreferred. In the in situ reaction the complex metal may be formed insitu, in the presence of a soap-forming carboxylic acid and the solublemetal salt which forms the insoluble soap. In the preferred procedure,the reaction products of the present invention are formed by thereaction of a water insoluble soap, a quinoline, a rosin amine, and awater soluble salt of a metal capable of forming a complex with ammonia.

Examples of the rosin amines which may be used to form the complex metalamine salt of a rosin amine of the present invention include the rosinamines made from wood or gum rosin or various modified wood or gumrosins, such as dehydrogenated (disproportionated) rosin, hydrogenatedrosin, or polymerized rosin. The rosin amines may also be the aminesderived from the pure rosin acids in which abietyl amine is the aminederived from abietic acid, dehydroabietyl amine is the amine derivedfrom dehydroabietic acid, dihydroabietyl amine is the amine derived fromdihydroabietic acid, and tetra'hydroabietyl amine is the amine derivedfrom tetrahydroabietic acid. And they may be the secondary tertiaryrosin amines in which the hydrogens attached to the nitrogen arereplaced by lower alkyl and alkylol groups,,

such as methyl dehydroabietyl amine, ethyl dehydroabietyl amine,dimethyl dehydroabietyl amine, diethyl. dehydroabietyl amine, isopropyldehydroabietyl amine, butyl dehydroabietyl amine, hydroxymethyl'dehydroabietyl amine, hydroxyethyl dehydroabietyl amine, and di(hyeighteen carbon atoms, and rosin.

ture of metals and a soap-forming acid or a mixture of.

such acids, Thus, the soaps may be soaps of calcium, barium, magnesium,mercury, lead, cadmium, silver, thallium, manganese, cobalt, nickel,chromium, iron, copper, .tin,-aluminum'an'd the like. The preferredsoaps are the copper, -zinc, chromium and nickel soaps because theresults obtained with these soaps are superior. to those obtainablewithrthe other soaps referred to herein.

- The soap-forming acids used in forming the aforesaid metal'soapsinclude caproic acid, caprylic acid, capric acid, ,lauric acid, myristicacid, palmistic acid, stearic acid, oleic acid, linoleic acid, linolenicacid, palmitoleic acid,

. melissic acid, hydroxystearic acid, ricinoleic acid, and the like, andmixtures thereof. ,The preferred soap-forming fatty acids or materialsare those saturated and unsaturated higheraliphatic acids containingfrom twelve to Other soap-forming fatty acids which may be used informing the metal soaps used in accordance with the present inventionare the mixed higher fatty acids derived from animal or vegetablesources such as, for example, sardine and other fish oils, lard, coconutoil, sesame oil, soybean oil, tung oil, 'corn oil or partially orcompletely hydrogenated derivatives of such oils, fatty acids derivedfrom carnauba, spermaceti, beeswax, candelilla wax and like waxes, andcarboxylic acids derived from petroleum or other hydrocarbons. Othersoap-forming acids which may be used arenaphthenic acid, tall oil fattyacids, and hydroaromatic acids Example 1 549 parts of 2-ethylhexoic acidare'mixed with 330 parts of dehydroabietyl amine at a temperature ofabout '300" F. and stirred. Heating and agitation are continued and 11parts of 8-hydroxyquinoline are added. To form the copper complex, 352parts of copper acetate are slowly added while stirring. After all ofthe copper has been added and is completely reacted (clear solution),

the temperature of the reaction mixture is slowly raised to 340 F. atwhich time there is added 55 parts of magnesium hexoate. Heating iscontinued until a clear solution is obtained and the charge is cooled toa temperature of about 175 F. and 260 parts of xylol are added toprovide a copper concentration of about 8%. The resulting composition isliquid at room temperature and the solvent may be adjusted to provideany concentration of the active ingredients as'desired.

'The reaction product of Example 1 appears to be the compound,cupri-magnesium dehydroabietyl ammine 8- hydroxyquinoliniumZ-ethylhexoate.

The composition of Example 1 was tested to determine its fungicidalactivity by treating duck samples with a xylol solution containing ofthe reaction product, as follows:

Samples of 10 oz. specification army' duck were cut'in- V then dried for24 hoursto obtainpomplete solvent r elease. The dried fabric pieces hada light greencolor,

The treated and dried pieces of duck were leached for V 24 hours inrunning water and buried horizontally in a well composted soilconsisting of 50% black loam and 50% pre-rotted manure, one-half inchbelow the soil surface. The moisture content of the soil was maintainedthe same time as the treated pieces and under the same,

conditions. The control was completely destroyed, being in the form ofsmall deterioratedpieces at the conclusion of the 28 day test period.

Prior to impregnating the piece of duck with the solution of Example 1,it and the untreated piece of duck were tested for tensile strengths ona 500 lb. vertical Scott tester. Each had a tensile strength of 296 lbs.After the 28 day burial period the treated duck and the control piecewere removed from the soil, washed thoroughly in warm water to removeall soil particles and airdried at room temperature. Tensile strength onthe'treated piece was then taken on the same Scott tester. It had atensile strengthof 298 lbs. The control piece was removed from the soilin small deteriorated pieces which had lost their fabric strength andhence were not tested. Each of these small pieces was badly stained. Incontrast the treated piece was substantially free from stain.

ExampleZ Example 1 was repeated except that 50 parts of isoqu'inolinewere used in lieu of the '8-hydroxyquinoline,

A test solution and fabric pieces were made up and tested :against anuntreated fabric control piece, as described. The treated pieces showedno sign of degradation and no loss of hand, whereas the control piecehad completely deteriorated.

Example 3 Example :1 was repeated except that 549 par-ts ofdihydroabietyl amine were used in lieu of the dehydroabietyl amine and60 parts of quinoline were used in lieu of the S-hydroxyquinoline. Atest solution and fabric pieces were made up and tested against anuntreated fabric control piece, as described. The treated pieces showedno sign of degradation and no loss of hand, whereas the control piecehad completely deteriorated.

Example 4 'Example 1 was repeated except that 66 parts ofS-methoxyquinoline were used in lieu of S-hydroxyquinoline. A testsolution and fabric pieces were made up and tested against an untreatedfabric control piece, as described. The treated pieces showed no sign ofdegradation and no loss of hand, whereas the control piece hadcompletely deteriorated.

Example5 Example 1 was repeated except that a corresponding 7 amount ofnickel Z-ethylhexoate was used in lieu of the soap of Example '1 and 66parts of 4-chloroquinoline were used in lieu of the 8-hydroxyquinoline.A test solut-ion and fabric pieces were made vup and tested against anuntreated fabric control piece, as described. The

treated pieces showed no sign of degradation and no loss 7 of hand,whereas the control piece had completely deteriorated.

Examples 6, 7, 8, 9 and 10 Example' l was repeated except that 352 partsof zinc acetate were used in lieu of the copper acetate. Example 1 wasrepeated except that 352 parts of mercury carbonate were used in lieu'of the copper acetate. Example 1 was repeated except that 352 parts ofnickel chloracet-ate were used in lieu of the copper acetate. Examthesedouble salts and fiabn'c pieces treated therewith were made up andtested against an untreated fia'bric control piece, as described. Thetreated pieces showed no sign of degradation and no loss of hand,whereas the control piece had completely deteriorated.

The reaction products of each of Examples 1 to 10, inclusive, in theform of the solutions described, were individually applied to woodsamples 1" x 3" and leather squares 2" x 6" by soaking under vacuum for20 minutes and drying for 6 hours, The treated specimens and untreatedcontrol specimens of similar dimensions were placed on a sterilenutrient agar medium with a pH of 5.5, which was used ifor thesubstratum in the petri dishes in which the specimens were placed. Eachtreated 'speciment and a control specimen were placed in'a single petridish. The specimens in each of these dishes were sprayed with a sporesuspension of the following organismskand incubated at 30 C. [for 14days: Chaetomium globosum, Penicillium citrinum, Aspergillus niger,Aspergillus ferreus, Trichoderma viride, and Aspergillus flavus.

At the conclusion of this test period it was found that fungi weregrowing over the entire surfiace of the leather 'and wood controlspecimens and that no growth existed on the treated wood and leatherspecimens.

The reaction products of the present invention can be used to treattextiles, papers, leather and the like by impregnating or coating thesematerials with a solution or dispersion of the reaction product in asuitable vehicle. Thus, the solutions described above may be used totreat these materials. These solutions may be compounded with resins,animal, vegetable and fish oils, plasticizers, flameproofing agents,driers, antioxidants and the like, in accordance withknown techniques,to impart to the solutions desired properties, For example,characteristics such as spread and flow of these solutions may bemodiiied by the addition thereto of a fiattyacid suchas launic acid,oleic acid,: linseed oil fatty acids, hempseed oil tatty acidsand likefatty acids having from 8 to 20 carbon atoms in the chain, and of atatty a-cidglycer-ide,

either raw or treated, such as raw or bodied linseed oil,

China wood oil, castor oil, dehydrated castor oil, and the like.Compatible natural and snythetic resins such as rosin, phenol-aldehyderesins, urea-aldehyde resins, vinyl resins and the like, or compatiblecellulose derivatives such as nitrocellulose, cellulose, celluloseacetate,

ethyl cellulose and the like may be incorporated in the solutions invarying proportions to meet any desired needs.

Plasticizers such as glycol, glycerine, pentaerythritol,

1 sorbitol, mannitol and other compatible plasticizers may be added tothe solutions. Suitable antioxidants which may be added to the solutionare phenyl salicy-late, tertiary butyl catechol and guaiacol, andsuitable driers are mine naphthenate, lead naphthen-ate, cobaltnaphthenate and zinc octoate.

It it is desired to impart water-proof properties to the solutions ofthe reaction products of the present invention, various waxes such asparaffin wax, bees wax, carnauba wax, spermaceti wax, synthetic waxes,and the like, may be incorporated in the solutions in varyingproportions to meet the desired needs.

By a proper choice of the solvents for the reaction products of thepresent invention and of suitable modifying agents, the resulting liquidcompositions may be controlled as to consistency, drying time, flow,penetration, and the like.

Other solvents for the reaction products of the present invention aretoluol, benzol, carbon tetrachloride, mineral spirits, naphtha, acetone,and the like. Any aliphatic or aromatic solvents, in general, may beused.

of the plants.

Compositions containing reaction products of the present invention notonly inhibit the growth of fungus organisms but may also kill theactivity of all existing fun- Textiles, leather, wood, resins,

able extent by soil animal life and these treated materials resist theaction of bacteria and insects. The reaction products of the presentinvention lend themselves for use as insecticides, in either dry orliquid form, and for preventing and combating diseases of plant life,both those diseases which attack the parts of plants above ground anddiseases such as rot which attack underground parts In dry form theactive ingredient is mixed with an inert diluent such as bentonite,kieselguhr, tal'c, etc.

While the present invention has been described in connection withcertain specific examples of methods ofmaking the reaction products, itis obvious that my invention is not to be construed as limited to thespecific materials disclosed in these examples or to the details of themethods set forth therein, since changes in materials, proportions andmethod details may be made without departing from the scope ofmyinvention as defined in the appended claims.

I claim:

1. The method of forming acomposition of matter comprising heating-at"an elevated temperature sufficient to place the reactants intohomogeneous solution below the lowest decomposition temperature of thereactants, a complex metal ammine salt of a rosin amine, said metal ofsaid salt being a metal whose salt is capable of forming a complex withammonia a water insoluble carboxylic acid soap and a quinoline selectedfrom the group con' sisting of quinoline, isoquinoline, a halogensubstituted quinoline, a nitroquinoline, an alkoxy quinoline and analkyl quinoline.

2. The product produced by the method of claim 1.

3. The method of forming a composition of matter comprising heating atanelevated temperature sufiicient to place the reactants intohomogeneous solution below the lowest decomposition temperature of thereactants, a rosin amine, a water soluble salt of a metal capable offorming a complex with ammonia, a water insoluble carboxylic acid soapand a quinolineselected from the group consisting of quinoline,isoquinoline, a halogen substituted quinoline, a nitroquinoline, analkoxy quinoline and an alkyl quinoline. f

-4. The method of forming a composition of matter comprising heating atan elevated temperature suflicient to place the reactants intohomogeneous solution below the lowest decomposition temperature of thereactants, dehydroabietyl amine, copper acetate, magnesium 2-ethylhexoate and 8-hydroxyquinoline.

5. The method of forming a composition of matter I complex metal amminesalt' of a rosin amine, said metal of sa1d salt being a metal whose saltis capable of forming a complex with ammonia awater insoluble carboxylicacid soap and isoquinoline I,

8. The product produced by the method of claim 7. 9. The method offorming a composition of matter comprising heating at an elevatedtemperature suflicient to place the reactants intohomogeneous solutionbelow 7 i a the lowest decomposition temperature of'the reactants, acomplex metal ammine salt of a rosin amine, said metal of said saltbeing ametal whose-salt is capable of form- ,ing'a complex with'ammoniaa water insoluble carboxylic facid soap and quinolinei 10. Theproduct produced byithe method of clairn9. 11. The method of forming acomposition of matter comprising heating at an. elevated temperaturesufficient toplacethe reactants into homogeneous solution below thelowest decompositiontemperature of the reactants, .a

complex metal'ammine, salt of, a rosin amine, said metal "of said saltbeing ainetal whose salt is capable of forminga complex with ammonia 'awater insolu'blecaboxylic' acid oapand an hydroxyquinoline. I V 112.-'Tl1e;method of forming a composition of matter comprising heatingat an elevated temperature sufficient to place the reactants intohomogeneous: solution below the lowest decompositiontemperature of thereactants,

' a complex nietal-ammine salt of a rosin amine, said metal 3 ofsaidsalt being a metal whose salt is capableof forming a complex withammonia a water insoluble carboxylic acid soap and quinaldine. r e

13; The method of forming a' compositmnof matter: I comprising heatingatan elevated temperature sufficient toiplade thereactants 'intohomogeneous solutionbelow the lowest decomposition temperature of thereaetants, a -eomplexmetal ammine-salt'ofa rosin amine,'said metal, 7 ofsaidsalt beinga metal whose salt iscapable of form-v ing a complexwith'a'mmonia a water insoluble. carboxylic acid soap and 4-chloroquinoline. 1

' 14. The method of -torrning av compositio V of matter comprisingheating ,at an elevated temperature suflicient to place thereacta'ntsinto homogeneous solution below the lowest decomposition temperature ofthe reactants; a

complex metal ammine 'salt ofa rosin amine, said metal 7 1s. The productmassed byjt method of cl a imlgl. 16. The method of forming aeomposition'of matter gcomprisingj heating at anelevatedtemperaturesufficient to place'the'ireactantsinto homogeneous solutionbelow,

-35 of said salt being a metalwhose salt is capable of forming a complexwith ammonia {a magnesium carboxylic' acidsoap and a quinolineselectedfrom the group consisting of 'quinoline, isoquinoline, a halogensubstituted .quinoline, a' n'itroquin line,;an alkoxy quinoline and analkyl quin olin e.

the,lowest-decomposition temperature of, the reactants,

a copper complex metal'lamrninersalt ofja rosin amine,

a magnesium carboxylic, acid I soap and 8 -hydroxyquino "lineflf" I l 5.17.}The1product. produced by thernethod of claim 16.

18. The methodjo'f formingtal composition. of matter comprisingheatingtat an elevated.temperaturesufficient .to ,place the reactantsinto homogeneous ,solu'tion below 7 the lowest decomposition temperatureOffthe reac,tants, !a l0 chromium complex metal aminine salt ofa rosinamine,

a magnesium carboxylic; acid soap and isoquinoline.

. 19. The product produced. by the method ofrclai n 1'8. 7 ZOIThemethcidof forming a composition or; matter comprising heating at an elevatedtemperature sufficient 15 toplacethe reactants into homogeneous solutionbelow the lowest. decomposition temperature of'the reactants, a eoppercoinplexmetzil amrnine salt. of 1a rosin, amine,

, a magnesium carboxylic acid'lsoap and 'q'uinoline; 1

ZL TheprQduct produced by thelm'etliodofclaiml20,

20, V 22 ,Ihe method of lf0r'ming1 a composition ofj-matter 1 place thereactants .jintqfhomogeneous.Jsolutionl. bElOW the lowest decompositiontemperature. sof thereactants,

,wcomplex 'metal' ammine salt era rosin ra'minegflsaid f 25 metal ofsaid salt being a metalwhose s'alt i's'capable'of forming a complex,with ammonia .a I'nnagnesiuiri' car 7 -boxy'lic acid soap a ndtanhydroxyqu olinef' 23. T eproducti roduced b y the ethod of 24. Themethod of forming a composition .of matter 7 '30 comprising heating atanelevated,temperaturesufiicient V to; place thesreactants intohoniogeneous' solution below "the loyvest decomposition temperature ofthe reactants,

' 'jde hydroabietyl amine, copper acetate magnesium 2-- ethylhexoateiandisoquinoline -r ltlatereneesCitedin-thefile this patent V, A, ,;,-UNITEDSTATES PATENTS 2490,924

W FOREI GNPATENIS -comprising heating at an. elevated jtempe'raturesufficient

1. THE METHOD OF FORMING A COMPOSITION OF MATTER COMPRISING HEATING ATAN ELEVATED TEMPERATURE SUFFICIENT TO PLACE THE REACTANTS INTOHOMOGENEOUS SOLUTION BELOW THE LOWEST DECOMPOSITION TEMPERATURE OF THEREACTANTS, A COMPLEX METAL AMMINE SALT OF A ROSIN AMINE, SAID METAL OFSAID SALT BEING A METAL WHOSE SALT IS CAPABLE OF FORMING A COMPLEX WITHAMMONIA A WATER INSOLUBLE CARBOXYLIC ACID SOAP AND A QUINOLINE SELECTEDFROM THE GROUP CONSISTING OF QUINOLINE, ISOQUINOLINE, THE HALOFENSUBSTITUTED QUINOLINE, A NITROQUINOLINE, AN ALKOXY QUINOLINE AND ANALKYL QUINOLINE.